Novel process for preparing oxymethylene polymer

ABSTRACT

Tetraoxane is polymerized by means of an electron acceptor substance used as polymerization initiator in the absence or presence of a saturated aliphatic carboxylic acid anhydride and/or an acetal, to obtain an oxymethylene polymer having thermal stability. An ionizing radiation or a light can, if desired, concomitantly be employed before and/or in the course of polymerization.

United States Patent [191 Yoshida et a].

[1-11 3,860,562 Jan; 14, 1975 NOVEL PROCESS FOR PREPARING OXYMETHYLENE POLYMER [75] Inventors: Masaru Yoshida; Yoshiaki Nakase; Akihiko Ito, all of Takasaki, Japan [73] Assignee: Japan Atomic Energy Research Institute, Tokyo, Japan [22] Filed: Dec. 18, 1972 [21] Appl. No.: 315,792

Related U.S.Application Data [63] Continuation-impart of Ser. No. 144,636, May 18,

1971, Pat. No. 3,719,637.

[30] Foreign Application Priority Data May 20, 1970 Japan 45-42381 July 4, 1970 Japan 45-58143 [52] U.S. Cl. 260/67 FP, 204/1592] [51] Int. Cl C08g l/20 [58] Field of Search 260/67 FP; 204/159.21

[56] References Cited UNITED STATES PATENTS 3,705,876 12/1972 Amann et al 260/67 FP 3,719,637 3/1973 Yoshida et al. 260/67 FP OTHER PUBLICATIONS c & En, Sept. 6, 1965, pp. 4041.

Primary Examiner-Lucille M. Phynes Attorney, Agent, or Firm-Stevens, Davis, Miller & Mosher [57] ABSTRACT 3 Claims, N0 Drawings t 1 NOVEL PROCESS FOR PREPARING OXYMETHYLENE POLYMER CROSS REFERENCE To THE COPENDING APPLICATION This is continuation in part to the Patent Application, entitled as Process for Polymerizing Tetraoxane, Ser. No. 144,636 filed on May 18, 1971, now U.S..Pat. No. 3,719,637.

BACKGROUND OF THE INVENTION easily depolymerized to formaldehyde. Therefore,.

these polymers require some stabilization treatment in order that they may be commercially practicable. According to one conventional process, a produced oxymethylene polymer is further treated with a carboxylic acid anhydride to be stabilized, but this process is disadvantageous in that many steps are required for the post-treatment. In another process, formaldehyde is polymerized in the presence of an anhydride of acarboxylic acid, but this process is disadvantageous in that the formaldehyde monomer must be highly purified before the polymerization in order to obtain asatisfactory result. v

It is known that tetraoxane is polymerized in the presence of a catalyst such as 8E (U.S. Pat. No. 3,457,226), but it is disadvantageous in that care must be taken in handling such a very reactive catalyst; in addition, such catalyst remaining in the product polymer has to be neutralized after polymerization is completed.

It is also known that trioxane is polymerized in the presence of an anhydride of aliphatic'carboxylic acids by means of an ionizing radiation (Japanese Pat. publication No. 26594/1963). In this process, the anhydride only serves to'enhance the polymerization rate of the unpurified trioxane and the thermal stability of the resulting polymer is not improved. Japanese Pat. publication No. 20309/ 1968 discloses a process for copolymerizing trioxane and itaconic anhydride in the presence of a peroxide catalyst; however, the resultant polymer lacks the properties required for an oxymethylene polymer. According to the process disclosed in Japanese Pat. publication No. 15629/1967, a somewhat thermally stabilized oxymethylene polymer is obtained by polymerizing trioxane and itaconic anhydride by means of an ionizing radiation, but the process is dis advantageous in that the polymerization rate is too slow. US. Pat. No. 3,346,663 discloses a process for polymerizing trioxane with an anhydride of organic acids in the presence of Lewis acids or Frie del-Crafts catalysts. However, the molecular-weight of'the' polymer is so low that the polymer is not adequate for practical use when an anhydride of organic acids is added to obtain a polymer having good heat stability.

The foregoing demerits in theprior art have been solved by the present invention, whereby thermally stabilized oxymethylene polymers are obtained with greater ease and in higher yield than when trioxane is polymerized, by polymerizing tetraoxane by means of a specific polymerization initiator. Incidentally, it is to be noted that a process for polymerizing trioxane can not always be applied to a process for polymerizing tetraoxane, since the reactivity of trioxane in the polymerization reaction differs from that of tetraoxane as described for example in U.S.'Pat. No. 3,457,226; French Pat. No. 1,424,655; J. Polymer Sci, B6, 727 (1964) and the like.

, A process for polymerizing a cyclic ether in the presence of maleic anhydride by means of an ionizing radiation or a radical initiator is disclosed in Japanese Pat.

publication No. 8829/1968, .the examples of which employ 3,3-bis-chloromethyl-oxetane or mixture thereof with trioxane. However, the resultant polymers have no thermal stability.

, It should be noted that trioxane can not be polymerized by using an electron acceptor compound as the polymerization initiator.

SUMMARY OF THE INVENTION An object of this invention is to provide a novel process for preparing an oxymethylene polymer which comprises polymerizing tetraoxane by means of an electron acceptor substance used as a polymerization initiator in the absence or presence of the additives such as a saturated aliphatic carboxylic acid anhydride and/or'an acetal. Another object ofthis invention is to provide a novel heat-stabilized oxymethylene polymer thus obtained. The other objects of this invention will become apparent in the following descriptions.

The process of this invention, if desired, can be carried out by the concomitant use of the'initiator and an ionizing'radiation or an ultraviolet light in advance of and/or in the course of polymerization.

In the radiation-induced polymerization of tetraox- "ane, no polymer was obtained in the molten phase or 'in solution (J. Polymer Sci. B1, 427 (1963)). However, in the case of the concomitant use, the polymerization is also carried out in liquid state. The concomitant use brings about a synergisticeffect on the rate of polymerization. In other words, the rate is much higher in the case of concomitant use than the sum of the rates where the initiator and radiation are applied in separate process. Therefore, the effect of ionizing radiation in the'presence of the initiators in this invention is essentially'different from that of thknown use of radiation.

The electron acceptors to be employed in this invention are substantially neutral and typically include qui-' nones (e.g., benzoquinone, p -chloroanil, etc.), nitriles (e.g., tetracyanoethylene, etc.), nitro-compounds (e.g., tetranitromethane, nitrobenzene, -m-dinitrobenzene, 1,3,5-tririitrobenzene, diphenylpicrylhydrazil, etc.), nitrogen-oxides (e.g., nitrous oxide, nitrogen monooxide, nitrogen dioxide, etc.) and sulfur hexafluoride. The electron acceptors also include an organic unsaturated ca'rboxylic acid anhydride having a hyperconjugated double bond (which means an organic-unsaturated carboxylic acid anhydride having an ethylenic double 'bond attached to at least one a'-carbon), such as maleic anhydride, itaconic anhydride, citraconic anhydride etc. However, these unsaturated anhydrides are sensitive to light or a radical initiator and may be polymerized to'some extent. It is not advisable to employ these anhydrides concomitantly with light or a radical polymerization initiator.

These additives serve to enhance the heat stability of the resulting polymer and in some cases to increase polymerization rate.

The saturated aliphatic carboxylic acid anhydrides to be employed as the additive preferably have aliphatic group of c about C and typically include acetic anhydride, propionic anhydride, butyric anhydride, succinic anhydride, etc.

The acetals to be employed as the additive in this invention are a cyclic acetal which excludes tetraoxane and trioxane, and an acyclic acetal. The cyclic acetal and acyclic acetal are represented by the following formulas (I) and (II) respectively:

. I I (I 0 wherein Q is a member selected from the group consisting of an unsubstituted or substituted aliphatic hydrocarbon residue having 2 to carbon atoms and an unsubstituted or substituted aliphatic hydrocarbon residue containing C-OC linkages and having 2 to 10 carbon atomsQthe substituent on the aliphatic hydrocarbon residue being selected from the group consisting of alkyl, alkenyl, phenyl, and halogens; and R and R each are members selected from the group consisting of a hydrogen atom or an aliphatic hydrocarbon residue having 1 to 3 carbon atoms;

R i-0 e. o-R .3 3

wherein R and R each are members selected'from the group consisting of an aliphatic hydrocarbon residue having 1 t0 4 carbon atoms and a substituted aliphatic hydrocarbon residue having 1 to 8 carbon atoms, the

substituent being selected from the group consisting of alkyl, alkoxy, and halogens; and R and R each are members selected from the group consisting of a hydrogen atom and an aliphatic hydrocarbon residue having 1 to 3 carbon atoms. 7

The acetals typically include consisting of dimethoxymethane (methylal), diethoxymethane (ethylal), l,ldimethoxyethane, 1,1-diethoxyethane, l,l-diethoxypropane, dipropoxymethane, dibutoxymethane, methoxybutoxymethane, l, l -dibutoxypropane, 1,1- diethoxybutane, 2,2-dimethoxypropane, 1,3-dioxolane, 1,3-dioxane, 1,3-dioxepane, l,3,-dioxecane, 1,3,5- tn'oxepane, 1,3,6-trioxocane, 4-methyl-l,3-dioxolane, 4-phenyll ,3 -dioxane, 5-et hyl-4-phenyl-1,3-dioxane, 4-methyl-4-phenyl-l ,3-dioxane, 2 methyl-4- methylene-1,3-dioxolane, l,3-dioxep-5-ene, 1,3- dioxen-6-ene, S-ethyl-l ,3-dioxep-5-ene, 2-ixopropyl-l ,3-dioxep-5-ene.

DESCRIPTION OF THE PREFERRED EMBODIMENTS In accordance with this invention, polymerization can be carried out as follows:

At least one species each of the initiator and if desired at least one species of the additive are added to tetraoxane. When the compound to be added is rather volatile, the polymerization system is confined in a sealed vessel. In the case of solid phase polymerization, the initiator and if desired the additive can be added to crystalline tetraoxane in the form of drops, spray or vapor, and if necessary then melt-mixed with tetraoxane and solidified. In liquid phase polymerization, they can be added to the liquid phase containing tetraoxane, or

and

mixed with crystalline tetraoxane and then melted or dissolved into a solution. The initiator and the additive can be added to tetraoxane simultaneously or separately by various ways. When two or more species of polymerization initiators or the additive are used, the order of addition, if necessary, may be determined by one skilled in the art according to the natures of the compounds tobe added.

The amount of initiator to be added depends on the species thereof, but is generally about l0 70 percent by weight, preferably about l0 10 percent by weight of tetraoxane. The amount of saturated carboxylic acid anhydride is about 10* 15 percent by weight, preferably about 10 5 percent by weight of tetraoxane. The amount of the acyclic acetal is about 10 5 percent, and that of the cyclic acetal is about 10' 10 percent by weight of tetraoxane. When theinitiator and/or the additive are solidsat room temperature or are used in low concentration, it is advantageous to use them in the form of a solution in a solvent inactive to the initiator, the additive and formaldehyde,

' such as benzene or n-hexane etc. The additive can be added to the polymerization system continuously or intermittently as it is consumed instead of charging the total amount from the start of polymerization.

When an ionizing radiation or an ultraviolet light is concomitantly employed, the results are substantially the same whether irradiation is effected before or after the polymerization initiator is added to the polymerization system. In the case of in-source polymerization, a dose rate of about 10 10 rad/hr is employed. The total dose in post-polymerization is generally about 10 10 rad. In the case of in-source polymerization (including light irradiation), the irradiation temperature is identical with that of polymerization. In the case of post-polymerization (including light irradiation), the irradiation temperature must be within the range in which tetraoxane is in the solid state. When irradiation is carried out at a temperature higher than C, insource polymerization proceeds except for the case in which the irradiation time is very short; post-polymerization can of course be effected thereafter. Incidentally, the useful radiations include alpha rays, beta rays, gamma rays, electron beam, X-rays, neutron beam, beams of heavy particles and mixtures thereof. An ultraviolet light from a mercury lamp etc. can also be utilized. 1

There is no special restriction in the polymerization temperature; it is generally at about 30- 150C, prefstriction, either, with respect to the atmosphere in which the polymerization is carried out; polymerization can be carried out either in air, vacuum or an inert gas. The term solid phase polymerization referred to herein means polymerization carried out when tetraoxane exists in the solid state (including dispersion), and

of an ionizing radiation or an ultraviolet light.

with a solvent such as acetone, benzene, etc. which is a good solvent for both tetraoxane and the additives so that the produced polymer may be separated from the' unreacted materials. 0

Now the invention is illustrated by way of working examples. These examples are included for better understanding of theinvention and should not be taken as limiting the scope of the invention. The product of each of the examples is a white crystalline substance. The viscosity number [1;] is determined with respect to a solution in p-chlorophenol containing 2 percent a-pinene at 60C. The thermal stability of the polymer is indicated as K (percent/minute) which means average thermal decomposition rate when the polymer is heated at 222C for 1 hour under nitrogen stream. The I amount of the additives is indicated in percentage on the basis of the weight of tetraoxane, unless otherwise specified.

EXAMPLE 1 A glass ampoule was charged with l g of tetraoxane purified by sublimation and 0.01 percent of ap-dioxane solution of various electron acceptors. The mixture was.

polymerized at l 10C for 4 hours, washed with acetone and dried, to obtain a white crystalline polymer. The results are shown in Table l.

A glass ampoule was charged with l g tetraoxane pu- I rified by sublimation and 10 percent of the following electron acceptor. The mixture was mechanically mixed and then polymerized for 10 minutes in 115C bath. Tetraoxane was polymerized before its melting, although the polymerization temperature 115C is higher than its melting point. The polymer was treated as in Example 1. The melting point of the polymer ranged between 168 169C. The yields were 30 percent, 64 and 61 percent respectively, when itaconic anhydride, maleic anhydride, and p-chloroanil were employed.

EXAMPLE 3 Example 2 was repeated except for changing the amount of electron acceptors. Thepolymerization was effected in solid phase. The results are shown in Table 2.

Table 2 The amount added Yield maleic anhydride 3o 82 7 do. 50 63 do. 44 pchloroanil 20 69 do. 30 83 do 50 91 EXAMPLE 4 A glass ampoule was charged with l g tetraoxane purified by sublimation and various amounts of diphenyl picryl hydrazil, which was disolved in p-dioxane and added in the amount of 10 1. After sealing the ampoules, the mixtures were polymerized for 4 hours in 110C bath and then treated as in Example 1. The results are shown in Table 3.

Example 4 was repeated except for changing polymerization temperature. Diphenyl picryl hydrazil was employed in the amount of 0.01 percent. The results are shown in table 4.

Table 4 Bath temp. 2 Hrs. polymerization 16 Hrs. polymerization (C) Yield(%) Yield(%) 1,

(liquid phase) In the polymerization at 130C, the polymerization system was at first in a transparent liquid phase, increased its viscosity and then separated white polymer.

EXAMPLE 6 A glass ampoule was charged with 1 g tetraoxane purified by sublimation and 0.1 percent of nitrogen oxide in gaseous state. After sealing the ampoule, polymerization was effected for 1 hour or 4 hours in 105C bath. When nitrous oxide was employed, the yields were 16 percent for 1 hour polymerization and 34 percent for 4 hours. When nitrogen monooxide was employed, the yields were 12 percent for 1 hour and 30 percent for 4 hours respectively.

EXAMPLE 7 Example 1 was repeated except for employing 0.01 percent of tetracyanoethylene. The polymer of [n] 1.0 was obtained in 18 percent yield for 1 hour polymerization at 1 10C. The polymer of [n] 1.3 was obtained in 40 percent yield for 4 hour polymerization at l 10C.

EXAMPLE 8 (control) The above examples were repeated using heating baths at 55C (solid phase) or 105C (liquid phase) for trioxane, except for employing trioxane instead of tetraoxane. No substantial polymer was obtained.

EXAMPLE 9 A glass ampoule was charged with 1 g tetraoxane purified by sublimation and 1.0 percent of propionic anhydride. The ampoule was added with 0.01 percent of 1,3,5-trinitrobenzene (initiator) and sealed. Polymerization was effected for 4 hours in 1 10C bath followed by treatment as in Example 1, to obtain a polymer of K 0.19 and [17] 0.5 in 77 percent yield.

EXAMPLE 10 Example 9 was repeated except for employing 0.01 percent of maleic anhydride as the initiator and an acetal such as methylal, 1,3-dioxolane or the mixture thereof as the additive. The results are shown in Table 5.

l. A process for preparing a heat-stabilized oxymethylene polymer, comprising polymerizing tetraoxane using p-chloranil as an electron acceptor substance. said p-chloranil being present in an amount of about 10 to percent by weight of the tetraoxane.

2. The process of claim 1 wherein acetic anhydride is present as an additive in an amount of about 10' to 15 percent by weight of the tetraoxane.

3. The process of claim 2 wherein the acetic anhydride is present in an amount of about 10" to 5 percent by weight of tetraoxane. 

2. The process of claim 1 wherein acetic anhydride is present as an additive in an amount of about 10 3 to 15 percent by weight of the tetraoxane.
 3. The process of claim 2 wherein the acetic anhydride is present in an amount of about 10 2 to 5 percent by weight of tetraoxane. 